US6372125B1 - Catalyst comprising a group VIB metal carbide, phosphorous and its use for hydrodesulphurisation and hydrogenation of gas oils - Google Patents
Catalyst comprising a group VIB metal carbide, phosphorous and its use for hydrodesulphurisation and hydrogenation of gas oils Download PDFInfo
- Publication number
- US6372125B1 US6372125B1 US09/643,863 US64386300A US6372125B1 US 6372125 B1 US6372125 B1 US 6372125B1 US 64386300 A US64386300 A US 64386300A US 6372125 B1 US6372125 B1 US 6372125B1
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- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 142
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000003921 oil Substances 0.000 title claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 title claims description 21
- 239000002184 metal Substances 0.000 title claims description 21
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 10
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 12
- 239000011159 matrix material Substances 0.000 claims abstract description 7
- 230000000737 periodic effect Effects 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 230000003197 catalytic effect Effects 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910021472 group 8 element Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000004523 catalytic cracking Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000001345 alkine derivatives Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 238000004939 coking Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 18
- 239000005864 Sulphur Substances 0.000 abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 37
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 230000032683 aging Effects 0.000 description 11
- 238000003483 aging Methods 0.000 description 11
- 229910017263 Mo—C Inorganic materials 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 10
- 238000010000 carbonizing Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 238000002161 passivation Methods 0.000 description 6
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- -1 VIB carbides Chemical class 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 150000001247 metal acetylides Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- DGUACJDPTAAFMP-UHFFFAOYSA-N 1,9-dimethyldibenzo[2,1-b:1',2'-d]thiophene Natural products S1C2=CC=CC(C)=C2C2=C1C=CC=C2C DGUACJDPTAAFMP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241001076960 Argon Species 0.000 description 1
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910020881 PMo12O40 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PCBMYXLJUKBODW-UHFFFAOYSA-N [Ru].ClOCl Chemical compound [Ru].ClOCl PCBMYXLJUKBODW-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012072 active phase Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000013876 argon Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
Definitions
- the present invention relates to a catalyst containing a carbide of at least one group VIB metal and phosphorous on an amorphous support, and to the use of this catalyst for hydrotreatment of hydrocarbon-containing, feeds with low sulphur contents.
- the present invention also relates to the field of fuel for internal combustion engines, more particularly the manufacture of a fuel for a compression ignition engine from a novel hydrotreatment catalyst phase.
- Gas oil cuts whether from distillation or from a conversion process such as catalytic cracking, currently contain non negligible quantities of aromatic, nitrogen-containing, and sulphur-containing compounds.
- the current legislation of the majority of industrialised countries requires that fuel which can be used in engines must contain less than 500 parts per million by weight (ppm) of sulphur. In the very near future, this maximum quantity will be reduced to 350 ppm in about 2000 and to 50 ppnm in about 2005 for the member states of the European Community.
- ppm parts per million by weight
- this maximum quantity will be reduced to 350 ppm in about 2000 and to 50 ppnm in about 2005 for the member states of the European Community.
- the amount of polyaromatic compounds in gas oils this may be reduced to a very low value (of the order of 1% to 2%) from 2005.
- hydrogenation of the polyaromatics contained in gas oil cuts is thus increasing in importance, because of the new sulphur and aromatic compound limits in this type of fuel.
- Desulphurisation is generally carried out under conditions and using catalysts which are not capable of simultaneously carrying out hydrogenation of the aromatic compounds.
- a first treatment of the cut must be carried out to reduce the sulphur content followed by a second treatment to hydrogenate the aromatic compounds contained in the cut.
- This second step is generally carried out by bringing the cut, in the presence of hydrogen, into contact with a catalyst generally based on a noble metal.
- the catalysts used must be able to operate in the presence of such compounds, which are powerful inhibitors of the activity of noble metals. It is thus important to seek out active phases having good thio-resistant properties.
- the aim of the present invention is thus to discover a novel catalyst based on a carbide which could be substituted for the noble metals used by the skilled person.
- the introduction of a quantity of phosphorous can substantially improve the activity of a catalyst containing at least one carbonized group VIB metal on an amorphous oxide support, preferably alumina or silica-alumina. Further, the activity of the catalyst is better if during preparation of the catalyst, a heteropolyanion type compound containing at least one group VIB element, phosphorous and group VIB elements introduced by any precursor is preferentially used.
- the catalyst can optionally contain at least one element from group VIII of the periodic table.
- Such a catalyst can advantageously carry out hydrodesulphurisation and hydrogenation of aromatic compounds in hydrocarbon-containing feeds containing sulphur-containing compounds.
- the invention also concerns the use of said catalyst for treating hydrocarbon-containing cuts containing sulphur and aromatic compounds and more particularly gas oil cuts from distilling crude oil and a variety of conversion processes such as cuts known as “cycle oils” from catalytic cracking processes.
- the catalyst of the present invention can be used for desulphurisation and hydrogenation of hydrocarbon-containing cuts.
- the feed which can be treated using the process of the invention has sulphur contents of less than 2000 ppm by weight, preferably 0.01 to 500 ppm by weight.
- this catalyst can also be suitable for any process aimed at hydrogenating all or a portion of the aromatic compounds of a feed containing traces of sulphur-containing compounds, such as hydrogenation of aromatic compounds in edible oils and in solvents.
- the catalyst of the present invention generally comprises, in weight % with respect to the total catalyst weight:
- the catalyst comprises phosphorous and a group VIB metal, such that the preferred P/VIB metal mole ratio is in the range 0.05 to 1.2, more preferably in the range 0.08 to 0.55.
- the catalyst is characterized in that the carbide phase is in the form of small particles with a size of less than 80 ⁇ , preferably less than 50 ⁇ and more preferably less than 30 ⁇ .
- the catalyst of the present invention can be prepared using any method which is well known to the skilled person.
- the catalyst of the present invention can be obtained using the following steps:
- a salt of a heteropolyanion containing at least one group VIB element and phosphorous and optionally at least one group VIII element more generally with formula AxByCzO n is used, where A is at least one group VIB element, B is a group VIII element, C is phosphorous and O is oxygen, where the ratios z(x+y) can be in the range 0.05 to 1.2, preferably in the range 0.08 to 0.55,
- Impregnation step a) can be carried out using any method which is well known to the skilled person.
- the components constituting the catalyst can be introduced separately into the catalyst, in successive addition steps using solutions of one or more elements, or simultaneously using a common solution of the elements.
- drying or activation (calcining or reduction) steps can be carried out between two successive impregnation steps.
- Drying step b) can be carried out using any method which is well known to the skilled person, at a maximum temperature of 150° C.
- Activation step c) consists of calcining in a neutral or oxidising mixture using any method which is well known to the skilled person at a temperature of more than 100° C. and less than 900° C.
- Reduction step d) consists of reduction in pure hydrogen or hydrogen mixed with an inert gas (for example argon) at a temperature of more than 100° C. and less than 900° C.
- an inert gas for example argon
- Step f) is a passivation step. Since this type of catalyst can be pyrophoric, a supplemental step is then necessary to avoid total oxidation of this catalyst. This step is generally carried out at ambient temperature (25° C.) by placing the catalyst under an inert gas then adding a low partial pressure of oxygen to that gas (1%) for periods of 1 to 15 hours.
- the amorphous oxide matrix is selected from transition aluminas, silicas and silica aluminas and mixtures thereof.
- This type of support has a specific surface area, determined using techniques which are known to the skilled person, in the range 100 to 600 m 2 /g, preferably in the range 150 to 500 m 2 /g.
- the amorphous oxide support can be used in the form of a powder or pre-formed in the form of beads or extrudates.
- Sources of group VIB elements which can be used are well known to he skilled person.
- preferred sources of molybdenum and tungsten which are used are oxides and ammonium salts are used such as ammonium molybdate, ammonium heptamolybdate and ammonium metatungstate.
- salts of heteropolyacids of group VIB metals such as phosphomolybdic acid or phosphotungstic acid are used.
- the precursors of group VIII metals which can be used are well known to the skilled person.
- nitrates, sulphates, phosphates, halides for example chlorides, bromides and fluorides, or carboxylates, for example acetates and carbonates.
- halides for example chlorides, nitrates, acids such as chloroplatinic acid, or chloroiridic acid, alkali metal chlorometallates, chloro-or hydroxo-amminated complexes, or oxychlorides such as ammoniacal ruthenium oxychloride.
- soluble co-ordination complexes in organic solvents, such as acetylacetonate complexes.
- carbonyl complexes for example, soluble co-ordination complexes in organic solvents, such as acetylacetonate complexes. It is also possible to use carbonyl complexes.
- the group VIII metal is selected from non-noble metals and preferably from nickel and cobalt.
- the hydrocarbons used for the carbonization step can be selected from alkanes, alkenes, alkynes, aromatic compounds or any other hydrocarbon-containing compound which is well known to the skilled person for its carbonizing properties. These hydrocarbons can be mixed with an inert gas or with hydrogen.
- the hydrodesulphurisation process of the invention is generally carried out at temperatures of 100° C. to 400° C., preferably 150° C. to 380° C.
- the operating pressure is generally 0.1 to 30 MPa, preferably 1 to 20 MPa.
- the space velocity, expressed as the volume of liquid feed treated per volume of catalyst per hour, is generally 0.1 to 20 h 1 ⁇ .
- the hydrogen/feed ratio used is expressed as the volume of hydrogen measured under normal conditions per volume of liquid feed; it is generally 50/1 to 2000/1.
- the feeds used generally contain at least 10% of aromatic compounds and less than 2000 ppm of S. They may be kerosines or gas oils from atmospheric distillation or feeds originating from refining processes such as catalytic cracking, coking, visbreaking, and hydroconversion of residues.
- Cylindrical extrudates 1.2 mm in diameter were thus obtained, with a specific surface area of 243 m 2 /g, a pore volume of 0.61 cm 3 /g and a unimodal pore size distribution centred on 10 nm.
- X ray diffraction analysis of the matrix revealed that it was solely composed of low crystallinity cubic gamma alumina.
- a sulphurised MoP/alumina catalyst was then prepared. Thirty grams of the alumina support of Example 1 were impregnated by nascent humidity, in one step, from a solution of ammonium heptamolybdate and phosphoric acid so as to deposit 13.5% by weight of MoO 3 and 2.66% by weight of P 2 O 5 on the alumina surface. After ageing, this sample was oven dried overnight at 80° C. The sample then underwent calcining in dry air at 500° C. for two hours. The catalyst was then sulphurised with a H 2 /H 2 S mixture containing 15% by volume of H 2 S at 350° C. for 2 hours. Reference catalyst MoP-S was thus obtained.
- a sulphurised CoMo/alumina catalyst was then prepared. Thirty grams of the alumina support of Example 1 were impregnated by nascent humidity, in one step, from a solution of ammonium heptamolybdate and cobalt nitrate so as to deposit 13.5% by weight of MoO 3 and 2.66% by weight of P 2 O 5 on the alumina surface. After ageing, this sample was oven dried overnight at 80° C. The sample then underwent calcining in dry air at 500° C. for two hours. The catalyst was then sulphurised with a H 2 /H 2 S mixture containing 15% by volume of H 2 S at 350° C. for 2 hours. Reference catalyst CoMo-S was thus obtained.
- a sulphurised CoMoP/alumina catalyst was then prepared. Thirty grams of the alumina support of Example 1 were impregnated by nascent humidity, in one step, from a solution of ammonium heptamolybdate, cobalt nitrate and phosphoric acid so as to deposit 13.5% by weight of MoO 4 ,4% by weight of CoO and 2.66% by weight of P 2 O 5 on the alumina surface. After ageing, this sample was oven dried overnight at 80° C. The sample then underwent calcining in dry air at 500 ° C. for two hours. The catalyst was then sulphurised with a H 2 /H 2 S mixture containing 15% by volume of H 2 S at 350° C. for 2 hours. Reference catalyst CoMoP-S was thus obtained.
- Example 1 Thirty grams of the alumina support of Example 1 were impregnated by nascent humidity, in one step, from a solution of ammonium heptamolybdate so as to deposit 13.5% by weight of MoO 3 on the alumina surface. After ageing, this sample was oven dried overnight at 80° C. The sample was then removed for carbonizing as follows: the temperature was raised at 60° C./h to 400° C. in argon to dry and reduce the catalyst, followed by a carbonizing step at a programmed temperature profile of 30° C./h to 677° C. in a stream of methane at atmospheric pressure. The catalyst was then cooled in a stream of argon to ambient temperature then treated in a stream of argon and 1% of oxygen for 15 hours to passivate it. Reference catalyst Mo-C was thus obtained.
- a carbonized CoMo/alumina catalyst was then prepared. Thirty grams of the alumina support of Example 1 were impregnated by nascent humidity, in one step, from a solution of ammonium heptamolybdate and cobalt nitrate so as to deposit 13.5% by weight of MoO 3 and 4% by weight of CoO on the alumina surface. After ageing, this sample was oven dried overnight at 80° C. The sample was then removed for carbonizing as follows: the temperature was raised at 60° C./h to 400° C. in argons to dry and reduce the catalyst, followed by a carbonizing step at a programmed temperature profile of 30° C./h to 677° C. in a stream of methane at atmospheric pressure. The catalyst was then cooled in a stream of argon to ambient temperature then treated in a stream of argon and 1% of oxygen for 15 hours to passivate it. Reference catalyst CoMo-C was thus obtained.
- a catalyst was prepared in the same manner as that described for Example 3 by impregnating the alumina of Example 1 with a solution of ammonium heptamolybdate and phosphoric acid so as to deposit 13.5% by weight of MoO 3 and 2.66% by weight of P 2 O 5 on the alumina surface.
- the non calcined sample underwent the same ageing, drying, carbonizing and passivation treatment as the sample of catalyst Mo-C of Example 3. Catalyst MoP-C was thus obtained.
- Catalyst CoMoP was then prepared.
- the alumina of Example 1 was impregnated with a solution of ammonium heptamolybdate, cobalt nitrate and phosphoric acid so as to deposit 13.5% by weight of MoO 3 , 4% by weight of CoO and 2.66% by weight of P 2 O 5 on the alumina surface.
- the non calcined sample underwent the same ageing, drying, carbonizing and passivation treatment as the sample of catalyst Mo-C of Example 3.
- Catalyst CoMoP-C1 was thus obtained.
- XRD analysis revealed that the catalyst contained no carbide particles with a size greater than 80 ⁇ .
- Example 4 In the same manner as that described for Example 4, a catalyst was prepared from the alumina of Example 1 by impregnation with commercially available phosphomolybdic acid H 3 PMo 12 O 40 solution. The non calcined sample underwent the same ageing, drying, carbonizing and passivation treatment as catalyst Mo-C of Example 3. Catalyst MoP-C2 was thus obtained. XRD analysis revealed that the catalyst contained no carbide particles with a size greater than 80 ⁇ .
- Example 4 In the same manner as that described for Example 4, a catalyst was prepared from the alumina of Example 1 by impregnation with a water-soluble heteropolyanion (NH 4 ) 6 P 2 Mo 5 O 23 . A portion of the sample was dried then underwent the same ageing, drying, carbonizing and passivation treatment as the sample of catalyst Mo-C of Example 3. Catalyst MoP-C3 was thus obtained. XRD analysis revealed that the catalyst contained no carbide particles with a size greater than 80 ⁇ .
- Example 4 In the same manner as that described for Example 4, a catalyst was prepared from the alumina of Example 1 by impregnation with a water-soluble heteropolyanion (NH 4 ) 6 P 2 Mo 18 O 62 . The dried sample underwent the same ageing, drying, carbonizing and passivation treatment as the sample of catalyst Mo-C of Example 3. Catalyst MoP-C4 was thus obtained. XRD analysis revealed that the catalyst contained no carbide particles with a size greater than 80 ⁇ .
- the catalysts of Examples 2 to 7 were tested for tetrahydronaphthalene hydrogenation at a total pressure of 40 bars and for a contact time of 0.4 seconds with 0.2 g of catalyst at 300° C.
- the test feed comprised tetrahydronaphthalene in n-heptane (nC 7 ).
- the catalytic activity, expressed as the moles of reactant transformed for identical catalyst quantities was measured after conversion stabilisation.
- the catalytic activity expressed in moles of reactant, namely tetrahydronaphthalene, transformed for identical catalyst quantities, was measured after conversion stabilisation.
- the catalysts from Examples 2 to 7 were tested for hydrodesulphurisation of a gas oil which had previously been hydrotreated containing 520 ppm S (feed GO-A) and 135 ppm S (feed GO-B) at a total pressure of 30 bars and at an hourly space velocity of 2.6 h ⁇ 1 with 40 cm 3 of catalyst at 340° C.
Abstract
Description
TABLE 1 | ||||
Catalytic activity | ||||
Ref. Catalyst | P/Mo | (mol/g catalyst/h) | ||
Mo-C | 0 | 6 | ||
Mo-S | 0 | 5 | ||
MoP-C1 | 0.4 | 10 | ||
MoP-C2 | 0.08 | 9 | ||
MoP-C3 | 0.4 | 13 | ||
MoP-C4 | 0.11 | 12 | ||
TABLE 2 | ||||
Catalytic activity | ||||
Ref. Catalyst | P/Mo | (mol/g catalyst/h) | ||
Mo-C | 0 | 3 | ||
Mo-S | 0 | 4 | ||
MoP-C1 | 0.4 | 5 | ||
MoP-C3 | 0.4 | 7.5 | ||
MoP-C4 | 0.11 | 7 | ||
TABLE 3 | |||
GO-A 520 ppm S | GO-B 135 ppm S | ||
HDS conversion (%) at | HDS conversion (%) at | ||
Ref. Catalyst | P/Mo | 340° C. | 340° C. |
Mo-C | 0 | 18 | — |
Mo-S | 0 | 12 | — |
MoP-C1 | 0.4 | 20 | 21 |
MoP-C3 | 0.4 | 20 | 23 |
MoP-C4 | 0.11 | 22 | 43 |
CoMoP-C4 | 0.4 | 81 | 67 |
CoMoP-C | 0.4 | 70 | 56 |
CoMoP-S | 0.4 | 65 | 53 |
TABLE 4 | ||||
Saturated hydrocarbon | ||||
4,6-DMDBT content | content | |||
P/Mo | (ppm) | mol % | ||
GO-B 135 ppm S | — | 25 | 72.5 |
MoP-C3 | 0.4 | 15 | 73.8 |
MoP-C4 | 0.11 | 18 | 73.5 |
Mo-S | 0 | 20 | 73.0 |
CoMoP-C4 | 0.11 | 17 | 74.8 |
CoMoP-S | 0.4 | 21 | 73.8 |
TABLE 5 | ||||
C content before | C content after | S content after | ||
Ref. Catalyst | P/Mo | test (weight %) | test (weight %) | test (weight %) |
Mo-C | 0 | 0.38 | 0.43 | 0.85 |
Mo-S | 0 | 0 | 2.1 | 6.2 |
MoP-S | 0.4 | 0 | 2.4 | 5.7 |
MoP-C1 | 0.4 | 0.44 | 0.46 | 0.7 |
MoP-C3 | 0.4 | 0.44 | 0.49 | 0.8 |
MoP-C4 | 0.11 | 0.43 | 0.47 | 0.6 |
Claims (22)
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US09/643,863 US6372125B1 (en) | 1999-08-23 | 2000-08-23 | Catalyst comprising a group VIB metal carbide, phosphorous and its use for hydrodesulphurisation and hydrogenation of gas oils |
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FR9910713 | 1999-08-23 | ||
FR9910713A FR2797785B1 (en) | 1999-08-23 | 1999-08-23 | CATALYST COMPRISING A PHOSPHORUS-CONTAINING GROUP VIB METAL CARBIDE AND USE THEREOF FOR HYDRODESULFURATION AND HYDROGENATION OF GASOLES |
US15812399P | 1999-10-08 | 1999-10-08 | |
US09/643,863 US6372125B1 (en) | 1999-08-23 | 2000-08-23 | Catalyst comprising a group VIB metal carbide, phosphorous and its use for hydrodesulphurisation and hydrogenation of gas oils |
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CN100363102C (en) * | 2005-06-15 | 2008-01-23 | 中国石油天然气股份有限公司 | Method for preparing transition metal carbide catalyst |
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